Professional Documents
Culture Documents
=
The species are given below, as copied to Excel from the output file is:
"Name" "Calc mol" #of H's vs. H2O or PO4-3
"H3PO4" 2.3383688598170800E-16 7.0151065794512400E-16 =+3*H3PO4
"OH-" 9.6145765999262200E-04 -9.6145765999262200E-04 =-1*OH-
"HPO4-2" 9.6114004614617200E-04 9.6114004614617200E-04 =+1*HPO4-2
"H2PO4-" 1.5879961785328100E-07 3.1759923570656200E-07 =+2*H2PO4-
H+ 1.0472800548262400E-11 1.0472800548262400E-11 =+1*H+
-4.1372413223813100E-12 =TotH
The value of TotH (Sum of protons gained minus the sum of protons lost, i.e., proton
balance, or TotH) is zero to within convergence error, either from the above Excel
addition or from Visual Minteq Equilibrated Mass Distribution window TotH = -
4.1372E-12 when I transferred data from the Output screen to Excel and re-added
them the sum was -2.38E-09, which is round off difference in the copy and transfer,
Mason Tomson Visual Minteq 11/2/2004 Acid/base Intro. Page 14
but when the default output file in the Visual Minteq folder (C:\vminteq\vmint.out) is
opened and all digits are saved the TotH value is exactly what is listed in the
Equilibrated mass distribution window, above. The value of TotPO4 component was
1.000E-03. That is, both mass balance conditions were satisfied! as required when
we instructed the program to use the Mass Balance equations to solve the problem,
because TotPO4 =0.001 M and TotH 0.00 convergence tolerance of 10
-4
of
TotComponent.
As can be seen from the top of the Output window, the solution is not electrically
neutral. That is to say, this solution can not be made up as simply phosphate, PO
4
3-
,
into water. If you added Na
+
=0.003 M as another component, you will get the same
answer, except that the solution will be electrically neutral, and the % Charge
difference box would be 0.0000 %. Try it. Also, if you select H+on the Main menu
in the components box and make the concentration 0.003 and click on Add to list:
and click on Run the pH =3.051, the pH of 0.001 M phosphoric acid in water since
TotPO4 =0.001 and TotH =0.003.
TotPO
4
=[PO
4
3-
] + [HPO
4
2-
] +[H
2
PO
4
1-
] +[H
3
PO
4
] =0.001 M and
TotH =1[HPO
4
2-
] +2[H
2
PO
4
1-
] +3[H
3
PO
4
] +1[H
+
] - 1[OH
-
] =0.003 M
Try it.
7. Example 7 mass and charge balance.VDA. Next, solve the same problem with the
same input data with pH Calc. from mass & charge balance selected:
a. Open Visual Minteq software, everything is initialized;
b. pH box click Calc. from mass & charge balance;
c. Ionic strength equal 0.00;
d. Component window select PO4; and concentration to 0.001;
e. Click add to list;
f. Click Run Minteq and OK:
Mason Tomson Visual Minteq 11/2/2004 Acid/base Intro. Page 15
The program will automatically open the Output Window and there are several things
to note in the top boxes in the Output window: the pH =3.051; Ionic Strength =0.00;
number of iterations =103; sum of cations =8.8896E-04 moles of charge/kg water (1
L); sum of anions is = 8.8896E-04 moles of charge/kg water; % dif. in cations vs.
anions is 0.000001 % (this is because we required charge balance equation to be
solved). What the computer solved was the mass balance equation for total
phosphate, TotPO4, plus the Charge balance equation for the solution. When all the
equilibrium constants are substituted in there are two equations, TotPO
4
and Charge
balance and two unknowns, [H
+
]
and [PO
4
3-
].
TotPO
4
=[PO
4
3-
] + [HPO
4
2-
] +[H
2
PO
4
1-
] +[H
3
PO
4
] =0.001 M and
ChargeBalance =Sum Cations Sum Anions =0.00
={1[H
+
]} {3[PO
4
3-
] +2[HPO
4
2-
] +1[H
2
PO
4
1-
] +1[OH
-
]} = 0.00
As you can see, since the charge balance equation has no strong acid anions, e.g.
NO
3
-
or Cl
-
, and no strong base cations, e.g., Na
+
or 2Ca
2+
, it is the same as having
added 0.001 M H
3
PO4 to the solution and then calculate the pH, pH =3.051. Note
also that the TotH component calculation, reported in the Equilibrated Mass
Distribution window is TotH =1[HPO
4
2-
] +2[H
2
PO
4
1-
] +3[H
3
PO
4
] +1[H
+
] -
1[OH
-
] =0.003000 M, although this equation was not used in the calculation,
because the charge balance option was selected and no strong base cations, Na
+
, were
added. If you add 0.003 M Na
+
to the component list on the Main menu, and use
Charge balance option to calculate the pH you will get pH = 10.978, as before. Try
it.
8. Example 8 Fixed pH. Commonly, as with a water analysis, you dont know all the
other strong base cation and anion concentrations very well, but you have a measured
pH value. At this point you enter a fixed pH in the pH box of e.g. 8.10 pH. Then
Mason Tomson Visual Minteq 11/2/2004 Acid/base Intro. Page 16
only the mass balance equations, excluding TotH, are solved with TotPO4 for the
species distributions. At this point the anion/cation imbalance is calculated and
reported from which you can calculate much strong base cations or strong acid anions
must be added for the solution to be neutral. Example for 0.001 M TotPO4 at 8.10
pH:
a. Open Visual Minteq software, everything is initialized;
b. pH box click Fixed at... and enter 8.10;
c. Ionic strength equal 0.00; units Molality;
d. Component window select PO4; and concentration to 0.001;
e. click add to list;
f. click Run Minteq and OK:
The program will automatically open the Output Window and there are several things
to note in the top boxes in the Output window: the pH =8.100; Ionic Strength =0.00;
number of iterations =0; sum of cations =7.9433E-09 moles of charge/kg water (1
L); sum of anions is = 1.8900E-03 moles of charge/kg water; % dif. in cations vs.
anions is 99.999159 %. What the computer solved was the mass balance equations
for total phosphate, TotPO4, using the 8.100 pH. After substituting in the equilibrium
constants, the free [PO
4
3-
] concentration is calculated see equations listed above:
TotPO
4
=[PO
4
3-
] + [HPO
4
2-
] +[H
2
PO
4
1-
] +[H
3
PO
4
] =0.001 M, or
[PO
4
3-
] =
+ + + 1
K
H
K K
H
K K K
H
001 . 0
3 3 2
2
3 2 1
3
=function of only pH
Mason Tomson Visual Minteq 11/2/2004 Acid/base Intro. Page 17
3 2 1
3
4
3
4
3
3 2
3
4
2 1
4 2
3
3
4
2
4
100 . 8
w w
K K K / ] PO [ ] H [ ] PO H [
K K / ] PO [ ] H [ ] PO H [
K / ] PO ][ H [ ] HPO [
10 / K ] H /[ K ] OH [
=
=
=
= =
+
+
+
+
The charge balance is not used, but it is computed from the above and reported at the
top of the Output menu and this is often valuable in various calculations.
ChargeBalance =Sum Cations Sum Anions =
={1[H
+
]} {3[PO
4
3-
] +2[HPO
4
2-
] +1[H
2
PO
4
1-
] +1[OH
-
]}
= 7.9433E-09 - 1.8900E-03
= -1.8900E-03
This means that to prepare a solution of TotPO4 =0.001 M at pH =8.100, you would
have to add 0.00189 M Na
+
or K
+
, etc., positively charged strong base cations to the
solution, e.g., as 0.00189 M NaOH or KOH to a solution of 0.001 M H
3
PO
4
. You
could write the formula as follows: 0.001 moles of Na
1.89
H
1.11
PO
4
per liter. Most
likely, what you would have done was to add 0.001 moles of H
3
PO
4
plus 0.00189
moles of NaOH per liter, at this point the net TotH =0.00111 moles of H
+
plus
0.00189 moles of Na
+
. See next section for verification.
9. Example 9 QC check.VDA. Check on the consistency of the calculations with the
Calc. from mass & charge balance option:
a. Open Visual Minteq software, everything is initialized;
b. pH box click Calc. from mass & charge balance;
c. Ionic strength equal 0.00; units Molality;
d. Component window select PO4; and concentration to 0.001; click add to list;
e. Select Na
+
and set concentration to 0.00189;
f. Click Run Minteq.
Mason Tomson Visual Minteq 11/2/2004 Acid/base Intro. Page 18
The program will automatically open the Output Window and there are several things
to note in the top boxes in the Output window: the pH =8.092 (approx. to 8.100);
Ionic Strength =0.00; number of iterations =26; sum of cations =1.8704E-03 moles
of charge/kg water (1 L); sum of anions is =1.8704E-03 moles of charge/kg water; %
dif. in cations vs. anions is 0.000008 %. The calculated pH would be exactly 8.100,
if you delete all Na-complexes in solution: on the Main menu you click on the drop
down menu Solid phases and excluded species and Specify excluded species,
then click on Aqueous species and select all species that are Na-complexes (such as
NaHPO
4
-
, etc.). Try it. What the computer solves is the mass balance equations for
total phosphate, TotPO4 =0.001 M, and the charge balance for the solution and since
TotNa =0.00189 M, this mass balance is also included. This approach can be
thought of as if TotPO4 is added as 0.001 M H
3
PO
4
and TotNa is added as NaOH.
10. Example 10 QC check.VDA. Check on the consistency of the calculations with the
Calculated from mass balance option:
a. Open Visual Minteq software, everything is initialized;
b. pH box click Calculated from mass balance;
c. Ionic strength equal 0.00; units Molality;
d. Component window select PO4; and concentration to 0.001; click add to list;
e. Select Na+and set concentration to 0.00189 and click on Add to list;
f. Select H+and set concentration to 0.00111 and click on Add to list;
g. Click Run Minteq and OK:
Mason Tomson Visual Minteq 11/2/2004 Acid/base Intro. Page 19
In the top boxes in the Output window: the pH =8.092; Ionic Strength =0.00; sum of
cations =1.8704E-03 moles of charge/kg water (1 L); sum of anions is =1.8704E-03
moles of charge/kg water, TotPO4 =0.00100 M, and the mass balance for TotH =
0.00111 M and mass balance for TotNa =0.00189 M. Essentially all the TotNa is in
solution as simply [Na
+
] ions, although the trace concentrations of complexes are
calculated and cause the pH to drop from 8.100 to 8.092.
11. Example 11 titration.VDA. Use the calculate pH from Calculated from mass
balance option, first:
a. Open Visual Minteq software, everything is initialized;
b. pH box click Calculated from mass balance;
c. Ionic strength equal 0.00; units Molality;
d. Component window select PO4; and concentration to 0.001; click add;
e. Select H
+
and set concentration to 0.00111 and click add;
f. Select Cl
-
and set concentration to 1E-8, or any small value, and click add this
will make the Cl
-
ion available to you to output the value of Cl
-
in the titration
(quirk of program);
g. Select Na
+
and set concentration to 0.00189 and click add;
h. Select tool bar Multiproblem/sweep;
i. Select titration box and click on the go to titration manager bar;
j. Click the Titration box, put 40 in State the number of titration steps, make volume
=1.00 L and volume of titrant =0.0001 L (0.1 ml or 0.1 meq./L per step);
k. Click the box Start addition on the 2
nd
step, this gives you the pH, etc. at the
start of the titration;
l. Type 1.00 in Concentration box and select H+1 and click on Save and Next and
select Cl-1 and Save and Next. Adjustments to number of titration points and
volume of titrant can be made to give finer looking titration.
Mason Tomson Visual Minteq 11/2/2004 Acid/base Intro. Page 20
m. Click Save and back to multisweep menu.;
n. Add Total dissolved Cl-1 and H+1, as below (the total dissolved option
includes the concentrations of titratnt that form complexes, in solution and is
generally what you want to use):
o. Click Save and Back;
p. Click Run Minteq and OK;
q. The output menu will appear. Note that the speciation for the 1
st
titration point
will be shown in the output screen; you can scroll down in the Select problem
No. box at the top middle and any of the 40 iteration points will be displayed.
r. Click on Select Sweep output and Print to Excel:
Plot the titration against Cl-1. In the Excel Sheet delete the second row and select
and move the pH data to the right of the H+column.
Mason Tomson Visual Minteq 11/2/2004 Acid/base Intro. Page 21
In the graph below, to put TotH on a second axis, click on the diamonds along the
bottom of the plot, click on Format, Selected data series, Axis, Secondary this scales
the second axis for the y-axis. The titration curve looks like the following after a
little more formatting of the axes.
Titration of 0.001 M TotPO4 starting at 8.1 pH
0
2
4
6
8
10
0 0.0005 0.001 0.0015 0.002
HCl M added
p
H
0
0.002
0.004
0.006
T
o
t
H
,
M
,
c
a
l
c
u
l
a
t
e
d
pH
H+1
The pH Calculated from mass balance and the Calc. from mass & charge
balance options will both work the same since the initial solution was made to be
the actual solution by initially adding TotH =0.00111 M and TotNa =0.00189 M.
The Calculated from mass balance used the TotH equation and added 0.0001 M
H
+
to each point and calculated the pH. The Calc. from mass & charge balance
option added 0.0001 M Cl
-
to the charge balance equation each time and calculated
the result, this method is much slower to converge and a couple of the points in latter
part of the calculation may not converge completely and might be marked, but they
will be very close. Try it.
12. Example 12a(b) titration with PCO2.VDA. Repeat the titration of 0.001 M
TotPO4 starting at 8.100 pH, but include P
CO2
=0.0005 atm.
1. Open Visual Minteq software, everything is initialized;
2. pH box click Fixed at... 8.100;
3. Ionic strength equal 0.00; units Molality;
4. Component window select PO4; and concentration to 0.001; click add;
Mason Tomson Visual Minteq 11/2/2004 Acid/base Intro. Page 22
5. Select Gases menu bar and set 0.0005 atm. and select Add and go back Main
menu;
6. Select Run Minteq, which will take you to the Output page with Sum of cations =
7.9433E-09 0 M (simply the [H+] concentration) and Sum of anions =
2.8539E-03 M, i.e., there is too little cations, such as Na
+
=2.8539E-03 M, in
solution. This is the end of Example 12a;
7. This is Example 12b. Select Na
+
and set concentration to 2.8539E-03 M and click
add, This is the amount of net Na
+
to make the solution charge balanced at the
starting point.
8. Select pH box Calc. from mass & charge balance;
9. Select Cl
-
and set concentration to 1E-8 and click add this will make the Cl
-
ion
available to you to output the value of Cl
-
in the titration (quirk of program), as
before;
10. Select tool bar Multiproblem/sweep and set the titration up, as above;
11. The Output menu will appear. Note that the speciation for the 1
st
titration point
will be shown in the output screen; you can scroll down in the Select problem
No. box at the top middle and any of the 40 iteration points will be displayed.
Select Sweep output and print to Excel. The following is the plot after a little
editing and putting TotCO3 and TotH on the secondary axis, as before.
Mason Tomson Visual Minteq 11/2/2004 Acid/base Intro. Page 23
0
2
4
6
8
10
0 0.001 0.002 0.003 0.004
HCl, M, added
0
0.001
0.002
0.003
0.004
0.005
pH TotCO3 SecAxis TotH SecAxis
Mason Tomson Visual Minteq 11/2/2004 Acid/base Intro. Page 24
13. Example 13a(b,c) Houston Tap Water.VDA. The following is an analysis of
Houston tap water, obtained from the City of Houston Water Quality Labs.
This is Example 13a. The following is the corresponding input into Visual Minteq,
using the left-most analysis and note that input concentrations have been input as
mg/l. The pH of 8.68 is used as a fixed pH and ionic strength has been calculated.
SiO2 is increased by the ratio of H
4
SiO
4
(96.1 g/mol)/SiO
2
(60.1 g/mol) since input is
as H
4
SiO
4
, not SiO
2
; TotCO3 input is as CO
3
=73 mg/l{CO
3
(60 g/mol)/HCO
3
(61
g/mol)} +6 mg/l ={71.8 +6 mg/l} =77.8 mg/l as CO
3.
Iron was assumed to be
TotFe(III) since the solution is probably aerated, but the results would not change
Mason Tomson Visual Minteq 11/2/2004 Acid/base Intro. Page 25
much if it were assumed to be TotFe(II) or equally divided, but the percentage to
precipitate would be quite different. Temp =62 F =16.67 C was used.
Click on Run Minteq and OK to Output screen:
The ionic strength is 4.3 mM, which would correspond to 251 mg/l as NaCl vs. the
observed value of 222 mg/l TDS, which is reasonable. The close agreement between
sum of cations and sum of anions is excellent and may suggest that they adjusted the
charge balance by adding Na
+
or K
+
to match or that the analyses are exceptionally
good in either case the analysis is quite self consistent.
Mason Tomson Visual Minteq 11/2/2004 Acid/base Intro. Page 26
The following is a listing to TotComponent for each component in the solution:
Note that TotH =1.2537E-03 is calculated, which is the proton balance of all species
relative to the Component that was entered.
This is Example 13b. Next, it is often necessary to raise the pH to some value to
precipitate the hardness ions, mostly TotCa and TotMg, and this is illustrated below
by allowing possible solid precipitates of Calcite (CaCO
3
), Brucite (Mg(OH)
2
), and
Ferrihydrate (Fe(OH)
3
). On the main menu Click on Solid Phases and Excluded
Species, Specify possible solid phases, then select calcite, brucite, and ferrihydrate.
Then, on the main menu select Run:
Mason Tomson Visual Minteq 11/2/2004 Acid/base Intro. Page 27
Now the ionic strength is 6.2 mM and Charge difference would require (8.76 mM
1.47 mM) =7.29 mM of strong base to be added. In the process of increasing the pH
most of the Ca, Mg, and Fe precipitate, as shown:
The new 12 pH equilibrium composition would be:
This is Example 13c. By keeping the Possible solids to precipitate, as above, and
performing a pH sweep from 7 to 12 pH would produce the following equilibrium
amounts of solids left in solution vs. pH.
1.E-07
1.E-06
1.E-05
1.E-04
1.E-03
1.E-02
7 8 9 10 11 12 13
1.E-11
1.E-10
1.E-09
1.E-08
1.E-07
TotCa+2 TotMg+2
TotCO3-2 TotFe+3SecAxis
Mason Tomson Visual Minteq 11/2/2004 Acid/base Intro. Page 28